Manganese doped barium titanate thin film compositions, capacitors, and methods of making thereof

ABSTRACT

The present invention is directed to a dielectric thin film composition comprising: (1) one or more barium/titanium-containing selected from (a) barium titanate, (b) any composition that can form barium titanate during firing, and (c) mixtures thereof; dissolved in (2) organic medium; and wherein said thin film composition is doped with 0.002 to 0.05 atom percent of a manganese-containing additive.

TECHNICAL FIELD

The present invention pertains to thin film capacitors, moreparticularly to thin film capacitors formed on copper foil that can beembedded in printed wiring boards (PWB) to provide capacitance fordecoupling and controlling voltage for integrated circuit die that aremounted on the printed wiring board package.

BACKGROUND

As semiconductor devices including integrated circuits (IC) operate athigher frequencies, higher data rates and lower voltages, noise in thepower and ground (return) lines and supplying sufficient current toaccommodate faster circuit switching becomes an increasingly importantproblem requiring low impedance in the power distribution system. Inorder to provide low noise, stable power to the IC, impedance inconventional circuits is reduced by the use of additional surface mounttechnology (SMT) capacitors interconnected in parallel. The higheroperating frequencies (higher IC switching speeds) mean that voltageresponse times to the IC must be faster. Lower operating voltagesrequire that allowable voltage variations (ripple) and noise becomesmaller. For example, as a microprocessor IC switches and begins anoperation, it calls for power to support the switching circuits. If theresponse time of the voltage supply is too slow, the microprocessor willexperience a voltage drop or power droop that will exceed the allowableripple voltage and noise margin and the IC will trigger false gates.Additionally, as the IC powers up, a slow response time will result inpower overshoot. Power droop and overshoot must be controlled withinallowable limits by the use of capacitors that are close enough to theIC that they provide or absorb power within the appropriate responsetime. This power droop and overshoot are maintained within the allowablelimits by the use of capacitors providing or absorbing power in theappropriate response time.

Capacitors for decoupling and dampening power droop or overshoot aregenerally placed as close to the IC as possible to improve theirperformance. Conventional designs have capacitors surface mounted on theprinted wiring board (PWB) clustered around the IC. In this case, largenumbers of capacitors requires complex electrical routing which leads toinductance. As frequencies increase and operating voltages continue todrop, power increases and higher capacitance has to be supplied atincreasingly lower inductance levels. A solution would be to incorporatea high capacitance density, thin film ceramic capacitor in the PWBpackage onto which the IC is mounted. A single layer ceramic capacitordirectly under the IC reduces the inductance to as minimum as possibleand the high capacitance density provides the capacitance to satisfy theIC requirements. Such a capacitor in the PWB can provide capacitance ata significantly quicker response time and lower inductance.

Embedding ceramic capacitor films in printed wiring boards is known.Capacitors are initially formed on metal foils by depositing a capacitordielectric material on the foil and annealing it at an elevatedtemperature. A top electrode is formed on the dielectric to form a firedcapacitor on foil structure. The foil is then bonded to an organiclaminate structure to create an inner layer panel wherein the capacitoris embedded in the panel. These inner layer panels are then stacked andconnected by interconnection circuitry, the stack of panels forming amultilayer printed wiring board.

A high capacitance density capacitor can be achieved by use of adielectric with a high permittivity or dielectric constant (K) and athin dielectric. High dielectric constants are well known inferroelectric ceramics. Ferroelectric dielectric materials with highdielectric constants include perovskites of the general formula ABO₃ inwhich the A site and B site can be occupied by one or more differentmetals. For example, high K is realized in crystalline barium titanate(BT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate(PLZT), lead magnesium niobate (PMN) and barium strontium titanate (BST)and these materials are commonly used in surface mount componentdevices. Barium titanate based compositions are particularly useful asthey have high dielectric constants and they are lead free.

Thin film capacitor dielectrics with a thickness of less than 1 micronare well known. Thin films can be deposited on to a substrate bysputtering, laser ablation, chemical vapor deposition, and chemicalsolution deposition. Initial deposition is either amorphous orcrystalline depending upon deposition conditions. Amorphous compositionshave low K (approximately 20) and have to be annealed at hightemperatures to induce crystallization and produce the desired high Kphase. The high K phase in barium titanate based dielectrics can only beachieved when grain sizes exceed 0.1 micron and so annealingtemperatures as high as 900° C. may be used.

Chemical solution deposition (CSD) techniques are commonly used to formthin film capacitors on metal foils. CSD techniques are desirable due totheir simplicity and low cost. High temperature annealing of bariumtitanate thin CSD films formed on base metal foils such as copper ornickel, require low oxygen partial pressures to avoid oxidation of themetal. The low oxygen partial pressures, however, often result in highleakage currents under applied bias (current densities) in bariumtitanate based compositions due to reduction of the dielectric material.In worst case situations, the capacitor may be shorted and dielectricproperties cannot be measured. This may be addressed by a subsequentre-oxidation procedure carried out at lower temperatures in which thedielectric and metal foil is exposed to higher partial pressures ofoxygen but this results in oxidation of the base metal foil.

A barium titanate CSD composition is disclosed in U.S. National patentapplication Ser. No. 10/621,796 (U.S. Patent Publication No.2005-001185). The composition is particularly suitable for forming highcapacitance density, ceramic films on copper foil. The precursorcomposition consists of the following chemicals: Barium acetate 2.6 gTitanium isopropoxide 2.9 ml Acetylacetone 2.0 ml Acetic acid 10.0 mlMethanol 15 ml

However, when annealed at 900° C. in a partial pressure of oxygen ofapproximately 10⁻¹¹ atmospheres, the film was conducting and are-oxidation procedure was necessary to produce parts from whichelectrical data could be taken. This procedure oxidized the foil and didnot necessarily produce optimum capacitor performance, particularly withrespect to leakage current density under bias. It is also not costeffective to re-oxidize the dielectric in a separate step. It would bean advantage, therefore, if the barium titanate composition could bedoped to produce good electrical performance, particularly a low leakagecurrent density under bias, immediately after the low oxygen partialpressure annealing process.

SUMMARY OF THE INVENTION

The present invention is directed to a dielectric thin film compositioncomprising: (1) one or more barium/titanium-containing selected from (a)barium titanate, (b) any composition that can form barium titanateduring firing, and (c) mixtures thereof; dissolved in (2) organicmedium; and wherein said thin film composition is doped with 0.002 to0.05 atom percent of a manganese-containing additive.

The present invention is further directed to a capacitor comprising thethin film composition detailed above wherein said thin film compositionhas been fired in a reducing atmosphere without the need forreoxidation. Furthermore, the present invention is also directed to aninnerlayer panel and a printed wiring board comprising such a capacitor.

In a further embodiment, the present invention is directed to a methodof making a capacitor comprising: providing a metallic foil; forming adielectric over the metallic foil, wherein forming the dielectriccomprises: forming a dielectric layer over the foil wherein thedielectric layer is formed from the composition noted above; annealingthe dielectric layer; and forming a conductive layer over thedielectric, wherein the metallic foil, the dielectric, and theconductive layer form the capacitor.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description will refer to the following drawings, whereinlike numerals refer to like elements, and wherein:

FIG. 1 is a block diagram illustrating a process for preparing aprecursor solution used to form a dielectric that does not require are-oxidation process.

FIG. 2 is a block diagram illustrating a process for making a capacitoron copper foil.

FIG. 3 is a graph showing capacitance density and loss tangent as afunction of voltage for pure barium titanate after re-oxidation.

FIG. 4 is a graph showing leakage current density as a function ofvoltage for undoped pure barium titanate after re-oxidation.

FIG. 5 is a graph showing capacitance density and loss tangent as afunction of voltage for 0.01 atom percent manganese doped bariumtitanate without re-oxidation.

FIG. 6 is a graph showing leakage current density as a function ofvoltage for 0.02 atom percent manganese doped barium titanate withoutre-oxidation.

FIG. 7 is a graph showing capacitance density and loss tangent as afunction of voltage for 0.02 atom percent manganese doped bariumtitanate without re-oxidation

FIG. 8 is a graph showing leakage current density as a function ofvoltage for 0.02 atom percent manganese doped barium titanate withoutre-oxidation.

FIG. 9 is a graph showing capacitance density and loss tangent as afunction of voltage for 0.04 atom percent manganese doped bariumtitanate without re-oxidation.

FIG. 10 is a graph showing leakage current density as a function ofvoltage for 0.04 atom percent manganese doped barium titanate withoutre-oxidation.

FIG. 11 is a graph showing capacitance density and loss tangent as afunction of voltage for 0.01 atom percent manganese doped bariumstrontium titanate without re-oxidation

FIG. 12 is a graph showing leakage current density as a function ofvoltage for 0.01 atom percent manganese doped barium strontium titanatewithout re-oxidation.

DETAILED DESCRIPTION

High capacitance density thin film dielectrics and methods of makingthereof are disclosed.

The manganese doped barium titanate dielectric according to the presentinvention may have essentially the same capacitance density and losstangent as undoped barium titanate after re-oxidation. The manganesedoped barium titanate dielectric when processed without a re-oxidationprocedure, however, has a much lower leakage current density under biasthan re-oxidized pure barium titanate.

BaTiO₃ is a preferred core material in the formation of high capacitancedensity dielectrics according to the present invention. However, metalcations with the oxide stoichiometry of MO₂ may also be used topartially or substantially substitute for titanium (e.g., Zr, Hf, Sn andmixtures thereof). While the terms “partially” and “substantially” arenot meant to be particularly limiting, there are various preferredembodiments. In one embodiment, “partially” is defined as up to andincluding 10 molar percent of the titanium. In one embodiment,“substantially” is defined as up to and including 50 molar percent ofthe titanium. These broaden the temperature dependence of capacitance atthe Curie point in the dielectric by “pinching” (shifting) the threephase transitions of BaTiO₃ closer to one another in temperature space.Metal cations having the oxide stoichiometry of MO (e.g., Pb, Ca, Sr andmixtures thereof) may also be used to partially or substantiallysubstitute for barium. While the terms “partially” and “substantially”are not meant to be particularly limiting, there are various preferredembodiments. In one embodiment, “partially” is defined herein as up toand including 10 molar percent of the barium. In one embodiment,“substantially” is defined as up to and including 50 molar percent ofthe barium. These cations shift the dielectric Curie point to higher orlower temperatures depending upon the material used.

According to a first embodiment, a high capacitance density thin filmCSD dielectric composition is disclosed that eliminates the requirementof a re-oxidation procedure after annealing the dielectric layer at atemperature in the range of approximately about 800 to 1050° C. under alow partial pressure of oxygen of less than about 10⁻⁸ atmospheres. Inone embodiment, a high capacitance density thin film CSD dielectriccomposition is disclosed that eliminates the requirement of are-oxidation procedure after annealing the dielectric layer at atemperature in the range of approximately about 900° C. under a lowpartial pressure of oxygen of approximately 10⁻¹¹ atmospheres.

Capacitors constructed according to the above method can be embeddedinto innerlayer panels, which may in turn be incorporated into printedwiring boards. The capacitors have high capacitance densities, low losstangents, and low leakage current densities under bias. Further, themethods according to the present invention may be practiced without theuse of a re-oxidation treatment while using environmentally desirablematerials.

Those skilled in the art will appreciate the above stated advantages andother advantages and benefits of various additional embodiments of theinvention upon reading the following detailed description of theembodiments with reference to the below-listed drawings.

According to common practice, the various features of the drawingsdiscussed below are not necessarily drawn to scale. Dimensions ofvarious features and elements in the drawings may be expanded or reducedto more clearly illustrate the embodiments of the invention.

The capacitor embodiment discussed herein has a dielectric thickness inthe range of about 0.4 to 1.0 μm with a capacitance density ofapproximately 2.5 μF/cm². Capacitors of this capacitance density rangehave a breakdown voltage in excess of about 20 volts.

Manganese doped crystalline barium titanate is used to form highpermittivity dielectric films or layers in the capacitor embodimentsdiscussed in this specification. Manganese doped crystalline bariumtitanate films enables high capacitance density devices to befabricated. The high capacitance density can be achieved usingdielectric thicknesses that are physically robust, preferably between0.4 to 1.0 μm. Manganese doping with as little as 250 ppm can be used tocreate the high dielectric constant dielectrics that are compatible withprocessing without re-oxidation procedures.

Chemical solution deposition (CSD) techniques may be used to form thedielectric. CSD techniques are desirable due to their simplicity and lowcost. The chemical precursor solution from which doped BaTiO₃ isprepared preferably contains barium acetate, titanium isopropoxide,acetylacetone, acetic acid, methanol, diethanolamine, and manganeseacetate tetrahydrate.

For a stable precursor solution, the above chemicals should be free ofwater. Water de-stabilizes the precursor composition, resulting inprecipitation of titanium oxide. It is therefore important to prepareand deposit the precursor solution in relatively low humidityenvironments, such as less than about 40 percent relative humidity. Oncethe precursor solution has been fully deposited on the metal foil anddried, it is less susceptible to humidity.

FIG. 1 is a block diagram illustrating a process for preparing aprecursor solution that will be used to form a dielectric according tothe present invention. In step S110, titanium isopropoxide is premixedwith acetyl acetone and heated. The premix can be done in, for example,a PYREX® container, and heating may take place on a hot plate with asurface temperature of about 90° C. In step S120, acetic acid is addedto the Ti isopropoxide/acetylacetone mixture. In step S130, bariumacetate and manganese acetate tetrahydrate is added into the container,and stirred until they are dissolved. In step S140, the solution isstirred while heated at 90° C. for a heating time of about 1 hour. Instep S150, methanol is added to the solution to yield approximately a0.3 molar concentration. The precursor solution is now suitable fordeposition.

FIG. 2 is a block diagram of a method suitable for forming a capacitoraccording to the present invention. The dielectric of the resultantcapacitor may be formed using the precursor solution discussed abovewith reference to FIG. 1. Variants of the methanol and the acetylacetonecomponents in the above-described precursor solution may also be used.For example, methanol may be substituted with acetic acid. Methanol mayalso be substituted by ethanol, isopropanol, acetone, butanol and otheralcohols. Acetylacetone may be substituted by ethanolamines such as3-ethanolamine, diethanolamine or monoethanolamine, for example.Titanium isopropoxide may also be substituted by titanium butoxide.

The deposition process illustrated in FIG. 2 is spin coating. Othercoating methods, such as dip or spray coating, are also feasible. Instep S210, a metallic foil may be cleaned. Cleaning is not alwaysnecessary but may be advisable. The metallic foil may be made fromcopper. Copper foils are desirable due their low cost and ease ofhandling. The copper foil will serve as a substrate on which a capacitoris built. The copper foil also acts as a capacitor “bottom” electrode inthe finished capacitor. In one embodiment, the substrate is an 18 μmthick electroless, bare copper foil. Other untreated foils, such as 1 ozcopper foil, are also suitable. Suitable cleaning conditions includeetching the foil for 30 seconds in a dilute solution of copper chloridein hydrochloric acid. The etching solution may be diluted approximately10,000 times from its concentrated form. The cleaning process removesthe excess oxide layer, fingerprints and other accumulated foreignmatter from the foil. If the copper foil is received from a vendor orother source in a substantially clean condition, and is handledcarefully and promptly used, the recommended cleaning process may not benecessary.

The copper foil is preferably not treated with organic additives.Organic additives are sometimes applied in order to enhance adhesion ofa metallic substrate to epoxy resins. Organic additives, however, maydegrade the dielectric film during annealing.

In step S220, the precursor solution discussed above with reference toFIG. 1 is deposited over the drum side (or “smooth side”) of the copperfoil substrate. The precursor solution may be applied using, forexample, a plastic syringe.

In step S230, the substrate is rotated for spin coating. A suitablerotation time and speed are 30 seconds at 3000 revolutions per minute.In step S240, the substrate is heat-treated. Heat treatment may beperformed, for example, at a temperature of 250° C. for five to tenminutes. Heat treatment is used to dry the precursor solution byevaporating solvents in the precursor solution. After heat treatment,the dried dielectric precursor layer is about 150 nm thick. Consecutivespinning steps may be used to coat the foil substrate to the desiredthickness. Three spinning steps, for example, may be used to produce afinal dried dielectric precursor thickness of approximately 0.5 μm.

In step S250, the coated substrate is annealed. Annealing first removesresidual organic material, and then sinters, densifies and crystallizesthe dried dielectric precursor. Annealing may be conducted in a hightemperature, low oxygen partial pressure environment. A suitable totalpressure environment is about 1 atmosphere. A suitable oxygen partialpressure is about 10⁻¹⁰ to 10⁻¹¹ atmospheres.

In step S250, the low oxygen partial pressure may be achieved bybubbling high purity nitrogen through a controlled temperature waterbath. Other gas combinations are also possible. In one embodiment, thefurnace temperature is at least about 900° C., and the oxygen partialpressure is approximately 10⁻¹¹ atmospheres. The water bath may be at atemperature of about 25° C. The annealing can be performed by insertingthe coated foil substrate into a furnace at temperatures below 250° C.The furnace is then ramped up to 900° C. at a rate of about 30°C./minute. The furnace is maintained at 900° C. for 30 minutes.

In step S260, the foil substrate is allowed to cool. Cooling may begoverned by a Newtonian profile, for example, created by simplyswitching the furnace off. Alternatively, the furnace temperature may beramped down at a specific rate. When the furnace temperature reachesabout 450° C., the foil substrate may be safely removed from the furnacewithout risk of undesired oxidation effects on the copper foil.Alternatively, the furnace may be allowed to return to room temperaturebefore the foil substrate is removed from the furnace.

In the low oxygen partial pressure annealing process, the copper foil isnot oxidized to Cu₂O or CuO. This resistance to oxidation is due to thelow oxygen pressure and high processing temperature. The dielectric isalso not reduced and maintains its good electrical characteristics,particularly a low leakage current density under bias. This resistanceto reduction is due to the manganese acceptor doping. With manganesedoping, conduction electrons are trapped by the manganese so that adecrease in insulation resistance and increase in dielectric losses aresuppressed.

The high temperature annealing of 900° C. described above fordensification and crystallization of the deposited dielectric providesdesirable physical properties and desirable electrical properties. Onedesirable physical property is a dense microstructure. Another desirablephysical property is resultant grain sizes between 0.1 μm and 0.2 μm.One desirable electrical property resulting from the grain size is acapacitance density in excess of 1 μF/cm². An additional desirableproperty is a low loss tangent, which may be less than 2.5 percent. Ingeneral, dielectric constants of polycrystalline BaTiO₃ based materialsfall precipitously when the average grain size falls below 0.1 μm, andgrain sizes of at least this order are therefore desirable.

In step 270, top electrodes are formed over the resulting dielectric.The top electrode can be formed by, for example, sputtering, combustionvapor deposition, electroless plating, printing or other suitabledeposition methods. In one embodiment, sputtered platinum electrodes areused. Other suitable materials for the top electrode include nickel,copper, and palladium. The top electrodes may be plated with copper toincrease thickness, if desired.

The following example illustrates the favorable properties indielectrics prepared according to the present invention, and thecapacitors incorporating the dielectrics.

EXAMPLE 1

A thin film un-doped pure barium titanate film was prepared on a copperfoil using a precursor as disclosed in U.S. National patent applicationSer. No. 10/621,796 (U.S. Patent Publication No. 2005-001185). Thecopper foil was coated with the dielectric precursor composition usingthe method outlined in FIG. 2. The composition of the dielectricprecursor was as given below: Barium acetate 2.6 g Titanium isopropoxide2.9 ml Acetylacetone 2.0 ml Acetic acid 10.0 ml Methanol 15 ml

Three spin coats were applied. The coated copper foil was annealed at900° C. for 30 minutes under a partial pressure of oxygen ofapproximately 10⁻¹¹ atmospheres. After annealing, the pure bariumtitanate was re-oxidized by placing the foil in a vacuum chamber underan atmosphere of approximately 10⁻⁵ Torr of oxygen at 550° C. for 30minutes. This condition was chosen to avoid significant oxidation of thecopper foil while still providing oxygen for re-oxidation of thedielectric. After re-oxidation, a top platinum electrode was sputteredon to the dielectric and the capacitance, dissipation factor and leakagecurrent density under bias could be measured.

As shown in FIG. 3, at zero bias, the capacitance density wasapproximately 2.5 μF/cm² and the loss tangent was approximately 5percent, but the pure barium titanate layer exhibited high leakagecurrent densities of the order of 1 amp per cm² under 10 volts bias asshown in FIG. 4.

EXAMPLE 2

A thin film 0.01 atom percent manganese doped barium titanate film wasprepared on a copper foil. The copper foil was coated with thedielectric precursor composition using the method outlined in FIG. 2.The composition of the dielectric precursor was as given below: Bariumacetate 5.08 g Titanium isopropoxide 5.68 ml Acetylacetone 3.86 mlAcetic acid 21 ml Methanol 24.26 ml Manganese acetate 0.002 gDiethanolamine 0.54 g

The only difference in inorganic levels between example 1 and example 2is the manganese. The diethanolamine is a stress reducing organicmaterial and has no effect on the final inorganic composition. Threespin coats were applied. The coated copper foil was annealed at 900° C.for 30 minutes at a partial pressure of oxygen of approximately 10⁻¹¹atmospheres. A top platinum electrode was sputtered on to the dielectricand the electrical characteristics of the capacitor were measured.

As shown in FIG. 5, the doped barium titanate layer without re-oxidationexhibited a similar capacitance density and loss tangent to that of there-oxidized pure barium titanate. However, as shown in FIG. 6, themanganese doped barium titanate without a re-oxidation showed a lowleakage current density of approximately 10 micro-amps per cm² at 10volts bias or approximately 10,000 times lower leakage current flowversus the re-oxidized undoped barium titanate.

EXAMPLE 3

A 0.02 atom percent manganese doped barium titanate thin film wasprepared on a copper foil in the similar manner described in EXAMPLE 1using the precursor solution described below except thecoating/pre-baking process was repeated six times. The manganese dopantsolution was prepared by dissolving Mn(OAc)₂ (0.2 g) in hot acetic acid(29.8 g): Barium acetate  2.0 g Titanium isopropoxide 2.22 gAcetylacetone 1.56 g Acetic acid 17.0 g Diethanolamine 0.21 g Manganesedopant solution 0.17 g

The capacitance density and loss tangent for a manganese doped bariumtitanate layer without re-oxidation are shown in FIG. 7. The capacitancedensity was approximately 1.4 μF/cm² at 0 volt and the loss tangent was<5 percent and the dissipation factor did not degrade under bias. Thelower capacitance density versus examples 1 and 2 were as a result oftwice the number of coatings giving a substantially thicker dielectric.As shown in FIG. 8, the 0.02 atom percent manganese doped bariumtitanate without an oxidation procedure showed a low leakage currentdensity of approximately 10 micro-amps/cm² at 10 volts bias orapproximately 1,000,000 times lower leakage current flow versus there-oxidized undoped barium titanate.

EXAMPLE 4

A 0.04 atom percent manganese doped barium titanate thin film wasprepared on a copper foil in the similar manner described in EXAMPLE 3using the precursor solution described below. The coating/pre-bakingprocess was repeated six times. The manganese dopant solution wasprepared by dissolving Mn(OAc)₂ (0.2 g) in hot acetic acid (29.8 g):Barium acetate  2.0 g Titanium isopropoxide 2.22 g Acetylacetone 1.56 gAcetic acid 17.0 g Diethanolamine 0.21 g Manganese dopant solution 0.42g

The capacitance density and loss tangent for a manganese doped bariumtitanate layer without re-oxidation are shown in FIG. 9. The capacitancedensity was approximately 1.3 μF/cm² at 0 volt and the loss tangent was≦8 percent and the dissipation factor did not degrade under bias. As inexample 3, the lower capacitance density was as a result of a thickerdielectric. As shown in FIG. 10, the 0.04 atom percent manganese dopedbarium titanate without an oxidation procedure showed a low leakagecurrent density of approximately 10 micro-amps/cm² at 10 volts bias orapproximately 1,000,000 times lower leakage current flow versus there-oxidized undoped barium titanate.

EXAMPLE 5

A 0.01 atom percent manganese doped barium strontium titanate(Ba_(0.65)Sr_(0.35)TiO₃) thin film was prepared on a copper foil in thesimilar manner described in EXAMPLE 3 except the strontium acetate wasalso added at the same time as the barium acetate using the precursorsolution described below. The coating/pre-baking process was repeatedsix times. The manganese dopant solution was prepared by dissolvingmanganese acetate tetrahydrate (0.29 g) in a mixture of acetic acid(27.71 g) and distilled water (2.0 g): Barium acetate 7.45 g Strontiumacetate 3.17 g Titanium isopropoxide 12.67 g  Acetylacetone 8.93 gAcetic acid 94.3 g Diethanolamine 1.17 g Manganese dopant solution 0.63g

The capacitance density and loss tangent for a manganese doped bariumstrontium titanate layer without re-oxidation are shown in FIG. 11. Thecapacitance density was approximately 1.2 μF/cm² at 0 volt and the losstangent was ≦3% and the dissipation factor did not degrade under bias.As in example 3, the lower capacitance density was as a result of athicker dielectric. As shown in FIG. 12, the 0.01 atom percent manganesedoped barium strontium titanate without an oxidation procedure showed alow leakage current density of approximately 1 mili-amps/cm² at 10 voltsbias or approximately 1,000 times lower leakage current flow versus there-oxidized undoped barium titanate.

1. A dielectric thin film composition comprising: (1) One or morebarium/titanium-containing additives selected from the group consistingof (a) barium titanate, (b) any composition that can form bariumtitanate during firing, and (c) mixtures thereof; dissolved in (2)organic medium; and wherein said thin film composition is doped with0.002 to 0.05 atom percent of a manganese-containing additive.
 2. Thecomposition of claim 1 wherein the barium in saidbarium/titanium-containing additive has been partially or substantiallyreplaced by one or more metal cations having the oxide stoichiometry ofMO wherein M is selected from the group consisting of (a) strontium; (b)lead; (c) calcium; and (d) mixtures thereof.
 3. The composition of claim1 wherein the titanium in said barium/titanium-containing additive hasbeen partially or substantially replaced by one or more metal cationshaving the oxide stoichiometry of MO₂ wherein M is selected from thegroup consisting of (a) zirconium; (b) hafnium; (c) tin; and (d)mixtures thereof.
 4. A capacitor comprising the thin film composition ofclaim 1 wherein said thin film composition has been fired in a reducingatmosphere without the need for reoxidation.
 5. An innerlayer panelcomprising the capacitor of claim
 4. 6. A printed wiring boardcomprising the capacitor of claim
 4. 7. A method of making a capacitorcomprising: providing a metallic foil; forming a dielectric over themetallic foil, wherein forming the dielectric comprises: forming adielectric layer over the foil wherein the dielectric layer is formedfrom the composition of claim 1; annealing the dielectric layer; andforming a conductive layer over the dielectric, wherein the metallicfoil, the dielectric, and the conductive layer form the capacitor. 8.The method of claim 7, wherein annealing comprises annealing at atemperature in the range of about 800 to 1050° C.
 9. The method of claim7, wherein annealing comprises annealing in an environment having anoxygen partial pressure of less than about 10⁻⁸ atmospheres.
 10. Themethod of claim 7, wherein annealing results in a dielectric comprisingcrystalline barium titanate or crystalline barium strontium titanate.11. The method of claim 7, wherein the capacitor has a capacitancedensity of at least 0.5 μF/cm².